CN101054007A - Automatic assembly organic-inorganic composite film for organic dyestuff and polyoxometalates - Google Patents
Automatic assembly organic-inorganic composite film for organic dyestuff and polyoxometalates Download PDFInfo
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- CN101054007A CN101054007A CN 200610074600 CN200610074600A CN101054007A CN 101054007 A CN101054007 A CN 101054007A CN 200610074600 CN200610074600 CN 200610074600 CN 200610074600 A CN200610074600 A CN 200610074600A CN 101054007 A CN101054007 A CN 101054007A
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Abstract
An organic-inorganic membrane is self-assembly by organic dye and polyoxometallate and relates to an organic-inorganic membrane and the manufacturing method of the same. The membrane is manufactured by XW12(x=B, Si, P)or[M4II(H20)(PW9O34)2]10-(M=Co, Cu, Zn, Mn)and organic dye of Bismarck Brown Y, Azure A and Basic Blue3 by means of a layer upon layer self-assembly method. The membrane has the abundant chemical properties of polyoxometallate and has the properties of organic dye, and has potential application prospect in the aspects of chemical modification electrode and optical material.
Description
Technical field
The present invention relates to a kind of organic, inorganic composite film, relate in particular to the organic and inorganic composite membrane of a kind of organic dyestuff and polyoxometallate self assembly.
Background technology
Along with the develop rapidly of electronics and information science, people are developed apace to the research of material science, and this also just requires device to need microminiaturization, multifunction, integrated etc.Yet single species is formed the material of preparation and is difficult to satisfy simultaneously multiple needs.And the organic and inorganic composite membrane carries out combination with organic matter and inorganic matter on molecular level, makes material promptly have the rigid nature that organic flexible characteristic has inorganic matter again.At present, the organic and inorganic composite membrane is owing to it has potential application and obtained extensive studies industrial.Organic dye molecule makes it have potential technology at nonlinear optics, holography, data storage and Organic Light Emitting Diode and uses owing to have the structural system of conjugation.Such as, organic dyestuff owing to very strong absorption is arranged at visible region, thereby the semi-conducting material that can sensitization has big bandwidth, this just makes them be applied in transform light energy.The cd-recordable (CD-R) that also has us to use, its recording layer mainly is that kind organic dye film is made.Polyoxometallate (Polyoxometalates, POMs), inorganic metal oxygen cluster compound as a quasi-representative has abundant structures, chemistry and performance physically, thereby it has important theoretical research value and wide application prospect in fields such as catalysis, medicine and materials chemistries.Yet the preparation of their these its films of potentiality application need.Self-assembly method is a kind of effective ways of constructing the organic and inorganic composite membrane layer by layer.This method alternately is immersed in anion and the cationic solution.Utilize self-assembly method layer by layer, as inorganic anion, simple chain organic matter is a cation, has prepared the organic self-assembled supermolecular film of a series of POMs-with POMs.But as far as we know, people are also relative less to the composite membrane research of organic dyestuff and polyoxometallate at present.In general, water miscible organic dyestuff all is to have the charged dye molecule of aromatic rings, and polyoxometallate is the big inorganic clusters compound that a class has negative electrical charge.
Summary of the invention
The objective of the invention is to prepare a kind of organic dyestuff and polyoxometallate and the organic and inorganic composite membrane.
The present invention is achieved by the following technical solutions, and method is as follows: at first, quartz glass plate or glass-carbon electrode are carried out cleaning treatment, clean with distilled water, nitrogen dries up; Quartz glass plate after will handling then or glass-carbon electrode are immersed in cationization in polymine (PEI) solution; Again 20min in solution that alternately is immersed in polyoxometallate (POMs) through the substrate of cationization and the organic dyestuff solution, each immerses and cleans with distilled water after step is taken out, nitrogen dries up, and this step that circulates can make the organic dyestuff-polyoxometallate composite membrane of the different numbers of plies.
The polyoxometallate that the present invention adopts is XW
12O
40(X=B, Si, P) or [M of Transition metal substituted
4II (H
2O)
2(PW
9O
34)
2]
10-u(M=Co, Cu, Zn, Mn).
Three kinds of cation organic dyestuff that the present invention adopts are Bismarck brown Y (BBY), Azure A (AzA), and its structural formula of Basic Blue 3 (BB3) is as follows.
Organic dyestuff-polyoxometallate the composite membrane of the present invention's preparation is synthetic first.This composite membrane promptly has the abundant chemical property of polyoxometallate, has the characteristics of organic dyestuff again, is a kind of compound film with multifunction; Especially use organic dyestuff as organic cation, this composite membrane is expected to be applied on optical material.
The specific embodiment
Embodiment 1:(BW
12/ BBY)
nThe preparation of multilayer organic and inorganic film
At first, quartz plate is cleaned: quartz glass plate is placed 98%H
2SO
4With 30%H
2O
2(7: in 80 ℃ of following impregnation process 40min, take out the back and clean in mixed liquor 3v/v) with distilled water; Immerse H again
2O: H
2O
2: NH
3=5: in 80 ℃ of following impregnation process 20min, take out the back and clean with distilled water in the mixed liquor of 1: 1 (v/v/v), nitrogen dries up, and promptly obtains the stand-by substrate of film forming.
Again substrate is carried out the PEI cationization: will immerse in the polymine PEI solution of 10mg/mL through the substrate of aforementioned processing program and place 20min, and take out the back and clean with distilled water, nitrogen dries up.
And then, alternately immerse 4.0 * 10 substrate through the PEI cationization
-2The BW of M
12Solution and 1.0 * 10
-3In the M BBY solution, place 20min respectively, each immerses and cleans with distilled water after step is taken out, and nitrogen dries up; The above step of repetitive cycling can make required (BW
12/ BBY)
nMultilayer organic and inorganic film.
The uv-vis spectra of film is characterized in the ultraviolet-visual spectrometer of the Lambda-35 type of U.S. PerkinElmer company production.Uv-vis spectra shows that the film of preparation in the increase linear along with the increase of the number of plies of the absorbance of wavelength 257nm and the BW12/BBY of 470nm place, illustrates that the film of preparation has the good homogeneous growth property.
The AFM of film is characterized in U.S. NanoScope IIIa, and (Digital Instruments Inc.), adopts the pattern, sweep limits 1.0 * 1.0 μ m of rapping
2Characterization result shows that film surface is all very even, (BW
12/ BBY)
4(BW
12/ BBY)
4-BW
12Roughness of film (RMS) is respectively 1.532nm and 2.022nm.Film (BW
12/ BBY)
4-BW
12Surface roughness is than (BW
12/ BBY)
4The successful preparation of film is described greatly.
Embodiment 2:([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ BBY)
nThe preparation of multilayer organic and inorganic film
Synthesis step and testing procedure are with reference to embodiment 1.Wherein the immersion solution of the substrate of PEI cationization adopts 5.0 * 10
-3[the Co of M
4 II(H
2O)
2(PW
9O
34)
2]
10-Solution.
Uv-vis spectra shows that the film of preparation is at wavelength 250nm and the [Co of 468nm place
4 II(H
2O)
2(PW
9O
34)
2]
10-The increase that the absorbance of/BBY is linear along with the increase of the number of plies illustrates that the film of preparation has the good homogeneous growth property.AFM characterization result explanation film surface is all very even, ([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ BBY)
4([Co
4II (H
2O)
2(PW
9O
34)
2]
10-/ BBY)
4-[Co
4 II(H
2O)
2(PW
9O
34)
2]
10-Roughness of film (RMS) is respectively 0.971nm, 1.694nm (1.0 * 1.0 μ m
2Film ([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ BBY)
4Surface roughness is than ([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ BBY)
4-[Co
4 II(H
2O)
2(PW
9O
34)
2]
10-The successful preparation of film is described greatly.
Embodiment 3:(BW
12/ AzA)
nThe preparation of multilayer organic and inorganic film
Synthesis step and testing procedure are with reference to embodiment 1.Wherein the immersion organic dyestuff of substrate adopts 0.5 * 10
-3M AzA solution.
Uv-vis spectra shows that the film of preparation is at wavelength 250nm, 285nm and the BW of 594nm place
12The increase that the absorbance of/AzA is linear along with the increase of the number of plies illustrates that the film of preparation has the good homogeneous growth property.
The AFM characterization result explanation film surface of film is all very even, (BW
12/ AzA)
4(BW
12/ AzA)
4-BW
12Roughness of film (RMS) is respectively 1.324nm, 1.715nm.Film (BW
12/ AzA)
4-BW
12Surface roughness is than (BW
12/ AzA)
4The successful preparation of film is described greatly.
Embodiment 4:([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ AzA)
nThe preparation of multilayer organic and inorganic film
Synthesis step and testing procedure are with reference to embodiment 3.Wherein the immersion solution of the substrate of PEI cationization adopts 5.0 * 10
-3[the Co of M
4 II(H
2O)
2(PW
9O
34)
2]
10-Solution.
Uv-vis spectra shows that the film of preparation is at wavelength 247nm, 285nm and the [Co of 584nm place
4II (H
2O)
2(PW
9O
34)
2]
10-The increase that the absorbance of/AzA is linear along with the increase of the number of plies illustrates that the film of preparation has the good homogeneous growth property.AFM characterization result explanation film surface is all very even, ([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ AzA)
4([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ AzA)
4-[Co
4 II(H
2O)
2(PW
9O
34)
2]
10-Roughness of film (RMS) is respectively 3.373nm, 4.845nm.Film ([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ AzA)
4Surface roughness is than ([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ AzA)
4-[Co
4 II(H
2O)
2(PW
9O
34)
2]
10-The successful preparation of film is described greatly.
Embodiment 5:(BW
12/ BB3)
nThe preparation of multilayer organic and inorganic film
Synthesis step and testing procedure are with reference to embodiment 1.Wherein the immersion organic dyestuff of substrate adopts 0.5 * 10
-3M BB3 solution.
Uv-vis spectra shows that the film of preparation is at wavelength 260nm, 615nm and the BW of 670nm place
12The absorbance of/BB3 increases along with the increase of the number of plies, illustrates that film successfully prepares.
The AFM characterization result explanation film surface of film is all very even, (BW
12/ BB3)
4-BW
12Roughness of film (RMS) is 3.154nm.
Embodiment 6:([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ BB3)
nThe preparation of multilayer organic and inorganic film
Synthesis step and testing procedure are with reference to embodiment 5.Wherein the immersion solution of the substrate of PEI cationization adopts 5.0 * 10
-3[the Co of M
4 II(H
2O)
2(PW
9O
34)
2]
10-Solution.
Uv-vis spectra shows that the film of preparation is at wavelength 255nm, 615nm and the [Co of 665nm place
4 II(H
2O)
2(PW
9O
34)
2]
10-The absorbance of/BB3 increases along with the increase of the number of plies, illustrates that film successfully prepares.
The AFM characterization result explanation film surface of film is all very even, ([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ BB3)
4-[Co
4II (H
2O)
2(PW
9O
34)
2]
10-Roughness of film (RMS) is 3.154nm.
Claims (8)
1. the organic and inorganic film of organic dyestuff and polyoxometallate self assembly, it is characterized in that: this film is by organic dyestuff Bismarck Brown Y or Azure A or Basic Blue 3 and polyoxometallate XW
12(X=B, Si P) form.
2. organic and inorganic film as claimed in claim 1 is characterized in that: described XW
12By [M
4 II(H
2O)
2(PW
9O
34)
2]
10-(Zn Mn) replaces for M=Co, Cu.
3. organic and inorganic film as claimed in claim 1 is characterized in that: this organic and inorganic film is (BW
12/ BBY)
nMultilayer organic and inorganic film.
4. organic and inorganic film as claimed in claim 1 is characterized in that: this organic and inorganic film is ([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ BBY)
nMultilayer organic and inorganic film.
5. organic and inorganic film as claimed in claim 1 is characterized in that: this organic and inorganic film is (BW
12/ AzA)
nMultilayer organic and inorganic film.
6. organic and inorganic film as claimed in claim 1 is characterized in that: this organic and inorganic film is (BW
12/ BB3)
nMultilayer organic and inorganic film.
7. organic and inorganic film as claimed in claim 2 is characterized in that: this organic and inorganic film is ([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ AzA)
nMultilayer organic and inorganic film.
8. organic and inorganic film as claimed in claim 2 is characterized in that: this organic and inorganic film is ([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ BB3)
nMultilayer organic and inorganic film.
Priority Applications (1)
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CN 200610074600 CN101054007A (en) | 2006-04-11 | 2006-04-11 | Automatic assembly organic-inorganic composite film for organic dyestuff and polyoxometalates |
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---|---|---|---|
CN 200610074600 CN101054007A (en) | 2006-04-11 | 2006-04-11 | Automatic assembly organic-inorganic composite film for organic dyestuff and polyoxometalates |
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CN101054007A true CN101054007A (en) | 2007-10-17 |
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ID=38794134
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104112820A (en) * | 2013-04-18 | 2014-10-22 | 东北师范大学 | Polyoxometallate-based composite film |
-
2006
- 2006-04-11 CN CN 200610074600 patent/CN101054007A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104112820A (en) * | 2013-04-18 | 2014-10-22 | 东北师范大学 | Polyoxometallate-based composite film |
CN104112820B (en) * | 2013-04-18 | 2017-08-25 | 东北师范大学 | A kind of laminated film based on polyoxometallate |
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Open date: 20071017 |